WO2018100798A1 - Capteur permettant de détecter une déformation d'une cellule secondaire étanche, cellule secondaire étanche, et procédé permettant de détecter une déformation d'une cellule secondaire étanche - Google Patents

Capteur permettant de détecter une déformation d'une cellule secondaire étanche, cellule secondaire étanche, et procédé permettant de détecter une déformation d'une cellule secondaire étanche Download PDF

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Publication number
WO2018100798A1
WO2018100798A1 PCT/JP2017/027240 JP2017027240W WO2018100798A1 WO 2018100798 A1 WO2018100798 A1 WO 2018100798A1 JP 2017027240 W JP2017027240 W JP 2017027240W WO 2018100798 A1 WO2018100798 A1 WO 2018100798A1
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secondary battery
sealed secondary
magnetic filler
coupling agent
detection sensor
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PCT/JP2017/027240
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English (en)
Japanese (ja)
Inventor
福田　武司
敏晃 河合
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東洋ゴム工業株式会社
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Publication of WO2018100798A1 publication Critical patent/WO2018100798A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G01B7/24—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in magnetic properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/213—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for cells having curved cross-section, e.g. round or elliptic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a sensor for detecting deformation of a sealed secondary battery, a sealed secondary battery to which the sensor is attached, and a method for detecting deformation of the sealed secondary battery.
  • sealed secondary batteries represented by lithium ion secondary batteries (hereinafter also simply referred to as “secondary batteries”) are not only mobile devices such as mobile phones and laptop computers but also electric vehicles such as electric vehicles and hybrid vehicles. It is also used as a power source for vehicles.
  • a single battery (cell) that constitutes a secondary battery includes an electrode group in which a positive electrode and a negative electrode are wound or stacked with a separator interposed therebetween, and an outer package that houses the electrode group.
  • a laminate film or a metal can is used as an exterior body, and an electrode group is accommodated together with an electrolytic solution in an enclosed space.
  • Secondary batteries are used in the form of battery modules or battery packs that include a plurality of single cells in applications where a high voltage is required, such as the power supply for electric vehicles described above.
  • a battery module a plurality of single cells connected in series are accommodated in a housing, and for example, four single cells are connected in two parallel two series or four series.
  • various devices such as a controller are accommodated in the casing in addition to the plurality of battery modules connected in series.
  • a battery pack housing is formed in a shape suitable for in-vehicle use.
  • Such a secondary battery has a problem that when the electrolytic solution is decomposed due to overcharge or the like, the unit cell expands as the internal pressure increases due to the decomposition gas, and the secondary battery is deformed. In that case, if the charging current or discharging current is not stopped, it will ignite and the secondary battery will burst as the worst result. Therefore, in order to prevent the secondary battery from bursting, it is important to detect the deformation of the secondary battery due to the swelling of the single cell with high sensitivity so that the charging current and the discharging current can be stopped in a timely manner.
  • Patent Document 1 includes a polymer matrix layer and a detection unit, and the polymer matrix layer includes a filler that changes the external field according to deformation of the polymer matrix layer.
  • a deformation detection sensor for a sealed secondary battery that is contained in a dispersed manner and in which the detection unit detects a change in the external field.
  • the deformation detection sensor detects a change in the magnetic matrix accompanying the deformation of the polymer matrix layer when the deformation of the secondary battery due to the swelling of the single cell causes the deformation of the polymer matrix layer containing the magnetic filler.
  • the deformation of the secondary battery is detected by the detecting unit.
  • the present invention provides a deformation detection sensor for a sealed secondary battery having higher sensitivity and excellent stability, a sealed secondary battery to which the sensor is attached, and a deformation detection method for the sealed secondary battery.
  • the deformation detection sensor of the sealed secondary battery of the present invention includes a polymer matrix layer and a detection unit, and the polymer matrix layer includes a polymer, a magnetic filler, and a coupling agent, The polymer forms a matrix of the polymer matrix layer, the magnetic filler changes the magnetic field according to the deformation of the polymer matrix layer, and the detection unit detects the change of the magnetic field.
  • the sealed secondary battery of the present invention is characterized in that the deformation detection sensor is attached.
  • the deformation detection method for a sealed secondary battery according to the present invention is characterized by using the deformation detection sensor.
  • the present invention it is possible to provide a deformation detection sensor for a sealed secondary battery, a sealed secondary battery, and a deformation detection method for the sealed secondary battery, which are more sensitive and excellent in stability.
  • the reason why the deformation detection sensor of the sealed secondary battery of the present invention has such an effect is not clear, but is considered as follows.
  • the sensitivity and stability of conventional deformation detection sensors are relatively low because the adhesion between the polymer and the magnetic filler is not sufficient, and the energy due to friction at the interface between the polymer and the magnetic filler when the polymer matrix layer is deformed. It is thought that the cause is that loss occurs or the followability of the magnetic filler is low.
  • the deformation detection sensor of the present invention is considered to improve the stability of the sensor by reducing the energy loss due to friction at the interface by improving the adhesion between the polymer and the magnetic filler as a matrix by the coupling agent. .
  • the sensor sensitivity is improved because the magnetic filler can easily follow the deformation of the polymer matrix layer.
  • FIG. 1 A perspective view schematically showing an example of a battery module Sectional drawing which shows typically the AA arrow cross section of FIG. Sectional drawing which shows another example of the attachment location of a polymer matrix layer
  • FIG. 1 is a perspective view of a battery module 1 having a deformation detection sensor (hereinafter, also simply referred to as “deformation detection sensor”) of a sealed secondary battery
  • FIG. 2 is a perspective view of the battery module 1 of FIG. It is A arrow sectional drawing.
  • the battery module 1 includes a housing 2, a single battery 3, and a deformation detection sensor 4.
  • the unit cell 3 is inside the housing 2, and the deformation detection sensor 4 is attached to the unit cell 3.
  • the deformation detection sensor 4 includes a polymer matrix layer 41 and a detection unit 42.
  • the polymer matrix layer 41 includes a polymer, a magnetic filler, and a coupling agent. The matrix of the polymer matrix layer 41 is formed, the magnetic filler changes the magnetic field according to the deformation of the polymer matrix layer 41, and the detection unit 42 detects the change of the magnetic field.
  • the battery module 1 is, for example, a lithium ion secondary battery that can be used as a power source for an electric vehicle, and is mounted on the vehicle in the form of a battery pack.
  • the plurality of battery modules 1 connected in series are housed in a casing together with various devices such as a controller.
  • the casing 2 of the battery pack is formed in a shape suitable for in-vehicle use, for example, a shape that matches the underfloor shape of the vehicle.
  • the sealed secondary battery 3 is not limited to a non-aqueous electrolyte secondary battery such as a lithium ion battery, and may be an aqueous electrolyte secondary battery such as a nickel metal hydride battery.
  • the unit cell 3 includes an electrode group formed by winding or laminating a positive electrode and a negative electrode with a separator between them, and an exterior body that accommodates the electrode group, and in an enclosed space inside the exterior body The electrode group is accommodated together with the electrolyte (not shown).
  • a laminate film such as an aluminum laminate foil is used for the outer package of the unit cell 3, but a cylindrical or square metal can may be used instead.
  • the polymer matrix layer 41 is affixed to the surface of the unit cell 3 (the outer surface of the exterior body), and an adhesive or an adhesive tape is used for the affixation as necessary.
  • the polymer matrix layer 41 is formed in a sheet shape, and is formed in a gap in the secondary battery, for example, in a gap between the adjacent single cells 3 or as shown in FIG. It is arranged between the body 2.
  • the polymer matrix layer 41 may be bent and attached to the corners of the unit cell 3 or the housing 2.
  • the polymer matrix layer 41 contains the magnetic filler that changes the magnetic field in accordance with the deformation of the polymer matrix layer 41.
  • the detection unit 42 detects a change in the magnetic field.
  • the detection unit 42 is disposed away from the polymer matrix layer 41 to such an extent that a change in magnetic field can be detected, and is preferably affixed to a relatively firm location that is not easily affected by the swelling of the unit cell 3.
  • the detection unit 42 is attached to the outer surface of the housing 2, but the present invention is not limited to this, and the detection unit 42 may be attached to the inner surface of the housing 2 or the battery pack housing. I do not care.
  • These cases are formed of, for example, metal or plastic, and a laminate film may be used for the case of the battery module.
  • the polymer matrix layer 41 is preferably mounted in a compressed state while being sandwiched in the gap of the deformation detection sensor 4.
  • the thickness of the polymer matrix layer 41 in an uncompressed state is larger than the gap G1 in which the polymer matrix layer 41 is disposed, and the polymer matrix layer 41 is compressed in the thickness direction.
  • the polymer matrix layer 41 shown in FIG. 3 is also sandwiched and mounted in the gap. In this example, the polymer matrix layer 41 is sandwiched and mounted in the gap between the unit cell 3 and the housing 2.
  • the thickness of the polymer matrix layer 41 in an uncompressed state is larger than the gap G2 in which the polymer matrix layer 41 is disposed, and the polymer matrix layer 41 is also preferably compressed in the thickness direction.
  • the thickness of the polymer matrix layer 41 in an uncompressed state is preferably 50 to 4000 ⁇ m, more preferably 100 to 3000 ⁇ m, and still more preferably 300 to 2500 ⁇ m.
  • the thickness is smaller than 50 ⁇ m, when an attempt is made to add the required amount of the magnetic filler, it tends to become brittle and the handling property tends to deteriorate.
  • the thickness is larger than 4000 ⁇ m, the polymer matrix layer 41 is excessively compressed and hardly deformed when disposed in the gap as described above, and the sensor sensitivity may be lowered.
  • the detection unit 42 When the unit cell 3 swells, the polymer matrix layer 41 is deformed accordingly, and a change in the magnetic field accompanying the deformation of the polymer matrix layer 41 is detected by the detection unit 42.
  • the detection signal output from the detection unit 42 is sent to a control device (not shown).
  • the detection signal connected to the control device (not shown) is connected.
  • the switching circuit cuts off the energization and stops the charging current or discharging current. In this way, deformation of the unit cell 3 is detected with high sensitivity, and explosion is prevented in advance.
  • the deformation detection sensor 4 does not press the unit cell 3 and the positional deviation is suppressed, so that the sensor characteristics are stabilized.
  • one polymer matrix layer 41 and one detection unit 42 are shown, but a plurality of them may be used depending on various conditions such as the shape and size of the unit cell 3. Good. At that time, the polymer matrix layer 41 attached as shown in FIG. 2 and the polymer matrix layer 41 attached as shown in FIG. 3 may coexist. Further, a plurality of polymer matrix layers 41 may be attached to the same unit cell 3, or a plurality of detectors 42 may be configured to detect changes in the external field due to deformation of the same polymer matrix layer 41. Good.
  • an elastomer component can be used, and the elastomer component can be arbitrarily used.
  • a thermoplastic elastomer, a thermosetting elastomer, or a mixture thereof can be used.
  • thermoplastic elastomer examples include styrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polybutadiene-based thermoplastic elastomer, polyisoprene-based thermoplastic elastomer, A fluororubber-based thermoplastic elastomer can be used.
  • thermosetting elastomer examples include polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, polychloroprene rubber, nitrile rubber, diene synthetic rubber such as ethylene-propylene rubber, ethylene-propylene rubber, butyl rubber, acrylic rubber, Non-diene synthetic rubbers such as polyurethane rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, and natural rubber can be mentioned.
  • a thermosetting elastomer is preferable because it can suppress the sag of the magnetic elastomer accompanying heat generation and overload of the battery. More preferred is polyurethane rubber (also referred to as polyurethane elastomer) or silicone rubber (also referred to as silicone elastomer).
  • the polyurethane elastomer is obtained by reacting an active hydrogen-containing compound with an isocyanate component.
  • an active hydrogen-containing compound and a magnetic filler are mixed, and an isocyanate component is mixed therein to obtain a mixed solution.
  • a liquid mixture can also be obtained by mixing a magnetic filler with an isocyanate component and mixing an active hydrogen-containing compound. The mixed liquid is poured into a mold subjected to a release treatment, and then heated to a curing temperature and cured to produce a magnetic elastomer.
  • a magnetic elastomer can be produced by adding a magnetic filler to a silicone elastomer precursor, mixing it, putting it in a mold, and then heating and curing it. In addition, you may add a solvent as needed.
  • isocyanate component that can be used in the polyurethane elastomer
  • compounds known in the field of polyurethane can be used.
  • the isocyanate component may be modified such as urethane modification, allophanate modification, biuret modification, and isocyanurate modification.
  • Preferred isocyanate components are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane disissocyanate, more preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate.
  • polyurethane those usually used in the technical field of polyurethane can be used.
  • Polyester polyol such as polyester polyol, polycaprolactone polyol, reaction product of polyester glycol and alkylene carbonate such as polycaprolactone, and the like, and the reaction of the resulting reaction mixture with organic polyol.
  • Polyester polycarbonate polyol reacted with dicarboxylic acid, esterification of polyhydroxyl compound and aryl carbonate High molecular weight polyol polycarbonate polyols obtained by the reaction can be mentioned. These may be used alone or in combination of two or more.
  • ethylene glycol 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, 1,4-bis (2-hydroxyethoxy) benzene, trimethylolpropane, glycerin, 1,2,6 -Hexanetriol, pentaerythritol, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose, 2,2,6,6-tetrakis (hydroxymethyl) cyclohexanol, and triethanol
  • Low molecular weight polyol component such as an amine, ethylenediamine
  • Preferred active hydrogen-containing compounds are polytetramethylene glycol, polypropylene glycol, a copolymer of propylene oxide and ethylene oxide, 3-methyl-1,5-pentane adipate, more preferably a copolymer of polypropylene glycol, propylene oxide and ethylene oxide. It is a coalescence.
  • a known catalyst that promotes the polyurethane reaction such as a tertiary amine catalyst or a metal catalyst may be used.
  • the tertiary amine include triethylenediamine (1,4-diazabicyclo [2,2,2] octane), N, N, N ′, N′-tetramethylhexanediamine, and bis (2-dimethylaminoethyl) ether. Etc. can be illustrated.
  • the metal catalyst include tin octylate, lead octylate, zinc octylate, bismuth octylate, and the like. These may be used alone or in combination of two or more.
  • the NCO index is preferably 0.3 to 1.2, more preferably 0.5 to 1.1, and still more preferably 0.7 to 1.05.
  • the NCO index is less than 0.3, the polyurethane tends to be insufficiently cured.
  • the NCO index is greater than 1.2, the elastic modulus increases and the sensor sensitivity tends to decrease.
  • the silicone elastomer to be used is not particularly limited, but a two-component heating type addition reaction type silicone elastomer is preferable from the viewpoint of dispersing the magnetic filler.
  • silicone elastomers KE-1204, KE-1031, KE-106, KE-109, KE-1281 (above, manufactured by Shin-Etsu Silicone), EE1840, SH850, SE1815CV, SE1816CV, SE9207, SE1740 (above, Toray Dow Corning).
  • the matrix of the polymer matrix layer 41 may be a foam containing bubbles or a non-foamed substance containing no bubbles.
  • the magnetic filler examples include rare earth-based, iron-based, cobalt-based, nickel-based, and oxide-based materials. From the viewpoint of adhesion to a polymer by a coupling agent, a rare-earth-based magnetic filler is preferable, and an iron atom A rare earth magnetic filler containing is more preferable. Examples of rare earth-based magnetic fillers containing iron atoms include NdFeB magnetic powder (Morcop Corp Magnequen Co., MQP-14-12), SmFeN magnetic powder, SmCo magnetic powder, and the like.
  • the shape of the magnetic filler is not particularly limited, and may be spherical, flat, needle-like, columnar, or indefinite.
  • the average particle size of the magnetic filler is preferably 0.02 to 500 ⁇ m, more preferably 0.1 to 400 ⁇ m, and still more preferably 0.5 to 300 ⁇ m. When the average particle size is smaller than 0.02 ⁇ m, the magnetic properties of the magnetic filler tend to be lowered, and when the average particle size exceeds 500 ⁇ m, the mechanical properties of the magnetic elastomer layer tend to be lowered and become brittle.
  • the content of the magnetic filler in the polymer matrix layer 41 is preferably 1 to 450 parts by weight, more preferably 2 to 400 parts by weight with respect to 100 parts by weight of the polymer. If it is less than 1 part by weight, it tends to be difficult to detect a change in the magnetic field, and if it exceeds 450 parts by weight, the polymer matrix layer 41 may become brittle.
  • the magnetic filler may be introduced into the matrix after magnetization, or may be magnetized while being introduced into the matrix. From the viewpoint of handling the magnetic filler, it is preferable to magnetize the magnetic filler while it is contained in the polymer matrix layer 41.
  • the method of magnetizing the magnetic filler is not particularly limited, and a commonly used magnetizing device, for example, “ES-10100-15SH” manufactured by Electromagnetic Industry Co., Ltd., “TM-YS4E” manufactured by Tamagawa Seisakusho Co., Ltd., Toei Industry Co., Ltd. It can be performed using “MPM-08” manufactured by Corporation. Usually, a magnetic field having a magnetic flux density of 1 to 4T is applied.
  • the magnetic filler may be included in a dispersed state in the matrix, or may be included in a state of being unevenly distributed in the thickness direction of the polymer matrix layer 41.
  • a method for unevenly distributing the filler for example, a method in which a magnetic filler is introduced into a polymer before curing and then allowed to stand at room temperature or a predetermined temperature, and then allowed to settle spontaneously depending on the weight of the magnetic filler can be used.
  • the filler uneven distribution ratio can be adjusted by changing the temperature and time to be performed.
  • the magnetic filler may be unevenly distributed using a physical force such as centrifugal force or magnetic force.
  • Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent, but a silane coupling agent is preferable from the viewpoint of improving the adhesion between the polymer and the magnetic filler.
  • Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Aminosilanes such as amines, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Epoxy silanes such as glycidoxypropylmethyldiethoxysilane, 3-glycidoxy
  • the content of the coupling agent in the polymer matrix layer 41 is preferably 0.0007 to 0.245 parts by weight, more preferably 0.0021 to 0.224 parts by weight with respect to 100 parts by weight of the polymer. Part. If the amount is less than 0.0007 parts by weight, the effect of the coupling agent tends to be difficult to obtain, and if it exceeds 0.245 parts by weight, the polymer tends to cause curing inhibition.
  • the coupling agent may be contained in the polymer matrix layer 41 in a state of being dispersed in a matrix, and the magnetic filler is surfaced with the coupling agent. It may be contained in the polymer matrix layer 41 by using the surface-treated magnetic filler. From the viewpoint of improving the adhesion between the polymer and the magnetic filler, it is preferable to use the magnetic filler surface-treated with the coupling agent.
  • the method for surface-treating the magnetic filler with the coupling agent is not particularly limited, and a surface treatment method usually used for a coupling agent can be applied.
  • a surface treatment method that is usually used for the silane coupling agent is a dry method in which the silane coupling agent is sprayed on the magnetic filler and then mixed.
  • a wet method in which the magnetic filler is dispersed in an organic solvent in which the magnetic filler and the silane coupling agent are dispersed and stirred, and the silane coupling agent is applied to the surface of the magnetic filler. From the viewpoint of more efficient reaction, a wet method is preferable.
  • Examples of the wet method include a silane coupling agent addition step (a1) for adding a silane coupling agent to an organic solvent in which the magnetic filler is dispersed, and a hydrolysis step (a2) for hydrolyzing the silane coupling agent.
  • a silane coupling agent addition step (a1) for adding a silane coupling agent to an organic solvent in which the magnetic filler is dispersed
  • a hydrolysis step (a2) for hydrolyzing the silane coupling agent.
  • the surface treatment method of the magnetic filler which has the heat processing process (a3) which heat-processes after a hydrolysis process which heat-processes after a hydrolysis process.
  • the organic solvent in which the magnetic filler is dispersed is not particularly limited, and examples thereof include toluene.
  • the silane coupling agent is hydrolyzed.
  • the method for adding water for hydrolyzing the silane coupling agent is not particularly limited.
  • the silane coupling agent is added in the silane coupling agent addition step (a1)
  • the water is dispersed in water. Examples thereof include a method of adding a silane coupling agent and a method of adding water to the organic solvent in which the magnetic filler and the silane coupling agent are dispersed after the silane coupling agent addition step (a1).
  • the addition amount of the silane coupling agent in the silane coupling agent addition step (a1) is preferably 0.001 to 0.35 parts by weight, more preferably 0.003 to 0, relative to 100 parts by weight of the magnetic filler. .32 parts by weight. If the amount is less than 0.001 part by weight, the effect of the coupling agent tends to be difficult to obtain, and if it exceeds 0.35 part by weight, it tends to cause inhibition of curing.
  • heating and drying are performed with a heater such as an electric furnace.
  • the heat treatment conditions are not particularly limited, and are, for example, 100 ° C. or higher and about 30 minutes to 3 hours.
  • the ratio of the number of silicon atoms to the number of iron atoms calculated from X-ray photoelectron spectroscopy (XPS) of the magnetic filler (number of silicon atoms / iron atom)
  • the number is preferably from 0.05 to 1.00, more preferably from 0.01 to 0.80, from the viewpoint of improving the adhesion between the polymer and the magnetic filler. More specifically, the ratio of the number of silicon atoms to the number of iron atoms is measured by the method described in Examples.
  • the surface of the magnetic filler is treated with a metal alkoxide. It is preferable to process.
  • the metal alkoxide is preferably one or more selected from the group consisting of titanium alkoxides and aluminum alkoxides, and more preferably titanium alkoxides from the viewpoint of improving the adhesion between the polymer and the magnetic filler.
  • titanium alkoxide examples include titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetra sec-butoxide, titanium tetra tert-butoxide, and the like.
  • Examples of the aluminum alkoxide include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum isopropoxide, aluminum butoxide, aluminum isobutoxide and the like.
  • the method for surface-treating the magnetic filler with the metal alkoxide is not particularly limited, and a surface treatment method usually used for metal alkoxide can be applied.
  • a surface treatment method usually used for metal alkoxide the metal alkoxide is sprayed on the magnetic filler and then mixed, or the magnetic filler is dispersed in an organic solvent, and the organic solvent in which the metal alkoxide is dispersed is described above.
  • distributes and stirs a magnetic filler is mentioned, The wet method is preferable from a viewpoint of making the said metal alkoxide react more efficiently on the surface of the said magnetic filler.
  • Examples of the wet method include a metal alkoxide addition step (b1) for adding a metal alkoxide to an organic solvent in which the magnetic filler is dispersed, a hydrolysis step (b2) for hydrolyzing the metal alkoxide, and after the hydrolysis step. And a magnetic filler surface treatment method having a heat treatment step (b3) of performing heat treatment.
  • the organic solvent in which the magnetic filler is dispersed is not particularly limited, and examples thereof include toluene.
  • the metal alkoxide is hydrolyzed.
  • the method for adding water for hydrolyzing the metal alkoxide is not particularly limited.
  • a method of adding the metal alkoxide dispersed in water Alternatively, after the metal alkoxide addition step (b1), there is a method of adding water to the organic solvent in which the magnetic filler and the metal alkoxide are dispersed.
  • the amount of the metal alkoxide added in the metal alkoxide addition step (b1) is preferably 0.005 to 0.50 parts by weight with respect to 100 parts by weight of the magnetic filler. If the amount is less than 0.005 parts by weight, the effect of the metal alkoxide tends to be difficult to obtain, and if it exceeds 0.50 parts by weight, it tends to cause inhibition of curing.
  • heating and drying are performed with a heater such as an electric furnace.
  • the heat treatment conditions are not particularly limited, and are, for example, 100 ° C. or higher and about 30 minutes to 3 hours.
  • the total number of atoms and the number of aluminum atoms / the number of iron atoms) is preferably 0.05 to 1.00, more preferably 0.10 to 0.80 from the viewpoint of improving the adhesion between the polymer and the magnetic filler. preferable.
  • the ratio between the total number of titanium atoms and the total number of aluminum atoms and the number of iron atoms is measured more specifically by the method described in the examples.
  • the detection unit 42 that detects a change in the magnetic field may be, for example, a magnetoresistive element, a Hall element, an inductor, an MI element, a fluxgate sensor, or the like.
  • the magnetoresistive element include a semiconductor compound magnetoresistive element, an anisotropic magnetoresistive element (AMR), a giant magnetoresistive element (GMR), and a tunnel magnetoresistive element (TMR).
  • AMR anisotropic magnetoresistive element
  • GMR giant magnetoresistive element
  • TMR tunnel magnetoresistive element
  • a Hall element is preferable because it is useful as the detection unit 42 having high sensitivity over a wide range.
  • the polymer matrix layer 41 is sandwiched in the gap between the adjacent unit cells 3 (see FIG. 2), and the polymer matrix layer 41 is sandwiched in the gap between the unit cell 3 and the housing 2 (see FIG. 2).
  • the present invention is not limited to this.
  • the polymer matrix layer may be sandwiched between the casing of a battery module included in the battery pack and the casing of the adjacent battery module, that is, within the gap between the casings of adjacent battery modules.
  • the polymer matrix layer may be sandwiched between the battery module housing and the battery pack housing.
  • the polymer matrix layer may be disposed in the unit cell, for example, between the positive electrode and the separator, between the negative electrode and the separator, or between the positive electrode and the outer package, between the negative electrode and the outer package, Furthermore, it may be disposed so as to be sandwiched between the separator and the outer package, and in particular, when used as a deformation detection sensor for a cylindrical or rectangular unit cell configured by winding a positive electrode / separator / negative electrode. Useful in.
  • Magnetic filler A1 130 parts by weight of toluene and 100 parts by weight of NdFeB magnetic powder (manufactured by Moricope Magnequench, MQP-14-12, average particle size 45 ⁇ m) were placed in a reaction vessel to prepare a magnetic filler dispersion A. Next, after mixing 0.00354 parts by weight of vinylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent, KBM-1003) and 1 part by weight of tetrahydrofuran, 0.00043 parts by weight of distilled water was added, and Stirring to obtain a mixture A.
  • vinylmethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent, KBM-1003
  • tetrahydrofuran 0.00043 parts by weight of distilled water was added, and Stirring to obtain a mixture A.
  • This liquid mixture A was added to the magnetic filler dispersion liquid A and subjected to a hydrolysis reaction at room temperature for 16 hours. Subsequently, the dispersion A was separated into a reaction solution and a magnetic filler by decantation, and then the reaction solution was removed. The remaining magnetic filler was washed three times with toluene, and heat-treated at 100 ° C. for 3 hours to obtain a magnetic filler A1 that had been treated with a silane coupling agent.
  • Magnetic fillers A2 to A8 Magnetic fillers A2 to A8 were obtained in the same manner as the magnetic filler A1, except that the type and amount of the silane coupling agent were changed to those shown in Table 1.
  • Magnetic filler B1 [Metal alkoxide treatment] 130 parts by weight of toluene and 100 parts by weight of NdFeB magnetic powder (manufactured by Moricope Magnequen Co., Ltd., MQP-14-12, average particle size 45 ⁇ m) were placed in a reaction container to prepare a magnetic filler dispersion B. Next, after mixing 0.00813 parts by weight of titanium tetrabutoxide (manufactured by Nacalai Tesque Co., Ltd.) and 1 part by weight of tetrahydrofuran, 0.00043 parts by weight of distilled water was added and stirred sufficiently to obtain a mixed solution B.
  • This liquid mixture B was added to the magnetic filler dispersion liquid B and allowed to undergo a hydrolysis reaction at room temperature for 16 hours. Subsequently, after the dispersion B was separated into a reaction solution and a magnetic filler by decantation, the reaction solution was removed. The remaining magnetic filler was washed three times with toluene, and heat-treated at 100 ° C. for 3 hours to obtain a magnetic filler b1 that had been treated with metal alkoxide.
  • the dispersion C was separated into a reaction solution and a magnetic filler by decantation, and then the reaction solution was removed.
  • the remaining magnetic filler was washed three times with toluene, and heat treated at 100 ° C. for 3 hours to obtain a magnetic filler B1 that had been treated with a silane coupling agent.
  • Magnetic fillers B2 and B3 Magnetic fillers B2 and B3 were obtained in the same manner as the magnetic filler B1 except that the type and amount of the silane coupling agent were changed to the contents shown in Table 1.
  • the ratio was calculated from the peak intensities of the detected peaks of Ti2p and Fe2p using the relative sensitivity coefficient method, and this was defined as the ratio of the number of titanium atoms to the number of iron atoms (Ti atom number / Fe atom number).
  • Al atom number / Fe atom number ratio The peak of the binding energy of Al2p and Fe2p is measured by the same method as the calculation of the Ti atom number / Fe atom number ratio, and the ratio is calculated using the relative sensitivity coefficient method from each peak intensity of the detected peak of Al2p and Fe2p.
  • the ratio of the number of aluminum atoms to the number of iron atoms (number of Al atoms / number of Fe atoms) can be determined.
  • Example 1 After adding 15.0 parts by weight of SE1740A (silicone elastomer manufactured by Toray Dow Corning) and 70.0 parts by weight of magnetic filler A1 treated with silane coupling agent to the reaction vessel, SE1740B (silicone elastomer manufactured by Toray Dow Corning) 15.0 parts by weight were added, and mixing and defoaming were performed with a rotation / revolution mixer (manufactured by Sinky Corporation).
  • This reaction solution was dropped onto a release-treated PET film having a 2.5 mm spacer and adjusted to a thickness of 2.5 mm with a nip roll. Then, it hardened
  • MPM-08 manufactured by Toei Kogyo Co., Ltd.
  • Examples 2 to 11 A polymer matrix layer was obtained in the same manner as in Example 1 except that the magnetic filler was changed to that shown in Table 2.
  • Example 12 In a reaction vessel, EX-3030 (polyoxypropylene glycol added with propylene oxide with glycerin as an initiator, OHV56, functional group number 3, manufactured by Asahi Glass Co., Ltd.) was put in 85.2 parts by weight, and vacuum dehydration was performed for 1 hour with stirring. It was. Thereafter, the inside of the reaction vessel was purged with nitrogen. Next, 14.8 parts by weight of Cosmonate T-100 (toluene diisocyanate, 2,4-form 100%, Mitsui Chemicals) was added to the reaction vessel, and the temperature in the reaction vessel was maintained at 80 ° C.
  • Econate T-100 toluene diisocyanate, 2,4-form 100%, Mitsui Chemicals
  • EX-3030 8.8 parts by weight of EX-2020 (polyoxypropylene glycol obtained by adding propylene oxide to propylene glycol as an initiator, OHV56, functional group number 2, manufactured by Asahi Glass Co., Ltd.) 25 (Nippon Kagaku Sangyo Co., Ltd. bismuth octylate solution, bismuth content 25%) 0.04 parts by weight of a mixed liquid was added 70 parts by weight of silane-coupled magnetic filler A4 to prepare a magnetic filler dispersion. .
  • Example 1 A polymer matrix layer was obtained in the same manner as in Example 1 except that NdFeB magnetic powder (manufactured by Moricope Magnequen Co., Ltd., MQP-14-12, average particle size 45 ⁇ m) that had not been surface-treated was used as the magnetic filler.
  • NdFeB magnetic powder manufactured by Moricope Magnequen Co., Ltd., MQP-14-12, average particle size 45 ⁇ m
  • the prepared polymer matrix layer was cut into a size of ⁇ 12 and attached to an aluminum plate having a thickness of 1 mm.
  • a Hall element (Asahi Kasei Electronics Co., Ltd., EQ-431L) was attached.
  • the autopolymer AG-X manufactured by Shimadzu Corporation is used to compress and deform for 5 cycles at a compression rate of 10 to 14% so that the magnetic polymer matrix is entirely compressed. It was.
  • the change in magnetic flux density is measured by the difference between the output voltage of the Hall element output at 10% compression deformation and the output voltage of the Hall element output at 12% compression deformation with respect to the thickness of the polymer matrix layer. Sensitivity was used. The measurement was performed 5 times and the average value was obtained. The average values obtained are shown in Table 2. The measurement temperature was 20 ° C. The larger the value, the higher the performance of the sensor.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measurement Of Length, Angles, Or The Like Using Electric Or Magnetic Means (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

L'invention concerne un capteur permettant de détecter une déformation d'une cellule secondaire étanche et pourvu d'une couche de matrice polymère et d'une partie de détection, la couche de matrice polymère comportant un polymère, une charge magnétique et un agent de couplage, le polymère formant la matrice de la couche de matrice polymère, la charge magnétique provoquant un changement d'un champ magnétique en réponse à la déformation de la couche de matrice polymère, et la partie de détection détectant le changement du champ magnétique. Grâce à ce capteur permettant de détecter une déformation d'une cellule secondaire étanche, il est possible de fournir un capteur permettant de détecter une déformation d'une cellule secondaire étanche qui a une sensibilité plus élevée et une excellente stabilité.
PCT/JP2017/027240 2016-11-30 2017-07-27 Capteur permettant de détecter une déformation d'une cellule secondaire étanche, cellule secondaire étanche, et procédé permettant de détecter une déformation d'une cellule secondaire étanche WO2018100798A1 (fr)

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CN109082253A (zh) * 2018-06-25 2018-12-25 南亚新材料科技股份有限公司 一种高分散性的无卤素粘合剂及其制备方法
WO2021131430A1 (fr) * 2019-12-24 2021-07-01 富士フイルム株式会社 Composition pour lentilles acoustiques, lentille acoustique, sonde à ondes acoustiques, sonde à ultrasons, appareil de mesure d'ondes acoustiques, système de diagnostic à ultrasons, appareil de mesure d'ondes photoacoustiques, endoscope à ultrasons et procédé de production de sonde à ondes acoustiques

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CN115863730B (zh) * 2021-09-27 2023-12-15 宁德时代新能源科技股份有限公司 夹具、夹持电池的方法、加热系统、电池加热及冷压方法

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WO2011029575A1 (fr) * 2009-09-08 2011-03-17 Carl Freudenberg Kg Capteur magnétique pour mousses
WO2015151331A1 (fr) * 2014-03-31 2015-10-08 東洋ゴム工業株式会社 Capteur de détection de déformation pour batterie secondaire scellée
JP2016099193A (ja) * 2014-11-20 2016-05-30 東洋ゴム工業株式会社 密閉型二次電池の変形検出センサの製造方法

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JP2006156423A (ja) * 2003-07-09 2006-06-15 Bridgestone Corp ゴム磁石シートおよびゴム磁石シートの製造方法
WO2011029575A1 (fr) * 2009-09-08 2011-03-17 Carl Freudenberg Kg Capteur magnétique pour mousses
WO2015151331A1 (fr) * 2014-03-31 2015-10-08 東洋ゴム工業株式会社 Capteur de détection de déformation pour batterie secondaire scellée
JP2016099193A (ja) * 2014-11-20 2016-05-30 東洋ゴム工業株式会社 密閉型二次電池の変形検出センサの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109082253A (zh) * 2018-06-25 2018-12-25 南亚新材料科技股份有限公司 一种高分散性的无卤素粘合剂及其制备方法
WO2021131430A1 (fr) * 2019-12-24 2021-07-01 富士フイルム株式会社 Composition pour lentilles acoustiques, lentille acoustique, sonde à ondes acoustiques, sonde à ultrasons, appareil de mesure d'ondes acoustiques, système de diagnostic à ultrasons, appareil de mesure d'ondes photoacoustiques, endoscope à ultrasons et procédé de production de sonde à ondes acoustiques
JPWO2021131430A1 (fr) * 2019-12-24 2021-07-01
JP7351929B2 (ja) 2019-12-24 2023-09-27 富士フイルム株式会社 音響レンズ用組成物、音響レンズ、音響波プローブ、超音波プローブ、音響波測定装置、超音波診断装置、光音響波測定装置及び超音波内視鏡並びに音響波プローブの製造方法

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